Composition of matter and process for resolving petroleum emulsions



Patented Apr. 18, 1939 ilNiTED stares FOR RESOLVING SIGNS PETROLEUMMelvin De Groote, University City, and Bernhard j Kaiser and Charles M.Blair, Jr., Webster Groves, Mos assignors to The Tret-O-Lite Company,Webster Groves, Ma,

of Missouri a corporation No Drawing. Application August 12, 1938,

Serial'No. 224,462

18 Claims.

This invention relates primarily to the treatment of emulsions ofmineral oil and water, such as petroleum emulsions, for the purpose ofseparating the oil from the water.

One object of our invention is to provide a novel process for resolvingpetroleum emulsions of the water-in-oil type, that are commonly referredto as cut oil, roily oil, "emulsified oil, etc., and which comprise finedroplets of naturally-occurring waters or brine's dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the emulsion.

Another object of our invention is to provide an economical and rapidprocess for separating emulsions which have been prepared undercontrolled conditions from mineral oil, such as crude petroleum andrelatively soft waters or weak brines. demulsification under theconditions just mentioned is of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

Another object of our invention is to provide a new material orcomposition of matter that is particularly adapted for use as ademulsifier in the resolution of crude oil emulsions, but which may haveuses in other arts that we have not yet investigated.

The new composition of matter which constitutes one feature of ourpresent invention consists of a certain kind of complex amine derived(a) by reaction between a dibasic carboxy acid body, such as phthalicanhydride, and (1)) simpier amines of the kind hereinafter described.Said new compound or composition of matter is particularly adapted foruse as a demulsifier for crude oil emulsions either alone or inadmixture with conventional demulsifying agents of a compatible type.

The process which constitutes the other feature of our present inventionconsists in subjecting a petroleum emulsion of the water-in-oil type tothe action of a demulsifying agent consisting of the new material orcomposition of matter above described, thereby causing the emulsion tobreak and separate into its component parts of oil and water or brinewhen the emulsion is permitted to remain in a quiescent state aftertreatment or is subjected to other equivalent separatory procedures.

Controlled emulsiflcation and subsequent Inasmuch as the demuisifyingagent employed in our process, constitutes a new chemical compound ornew composition of matter, we deem it advisable to describe the rawmaterials entering into the manufacture of the same, as well as themethod of manufacture.

One can obtain or manufacture chemical compounds whose composition isindicated by the following formulas:

T OILRCOOJH W ical, such as a CaHs radical, C4Ha radical, etc..

and therefore the above formula may be rewritten: V

(0H.RC0O.CuHh)- where n'represents a small whole number preferably notover.10.

In the above formulas, T represents a nonhydroxy aliphatic hydrocarbonradical, such as a methyl, ethyl, propyl, amyl, or similar radical; or Tmay represent a. non-hydro alicyclic radical,

such as a cy'clohexyl radical, or a non-=hydroxy aralkyl radical, suchas a benzyl radical; or the acylated radical obtained by replacing ahydrogen atom of the hydroxyl group of an alkylol radical by the acylradical of a monobasic carboxy acid, such as acetic acid, butyric acid,oleic acid, stearic acid, naphthenic acid, abietic acid, or the like,all of which are characterized by having less than 32 carbon atoms. Thealkylol radical prior to acylation may be a hydroxy alicyclic or ahydroxy aralkyl radical, provided that the hydroxy radical is attachedto the aliphatic residue of the aralkyl radical. In the above formulas,OHRCOOH represents a hydroxylated fatty acid, such as ricinoleic acid,hydroxystearic acid, dihydroxystearic acid, diricinoleic acid,triricinoleic acid, polyricinoleic acid, etc. and OHRCOO represents theoxy acyl radical derived from such acid, he, the ordinary acid radical.Blown oils (oxidized oils) are not included.

As to the amines above described which happen to be tertiary amines, itmay be well to point out that these may be formed readily by a reactioninvolving an ester of the hydroxylated fatty acid and a correspondingamine.

Reference is made to copending application for patent, Ser. No. 180,993,filed December 21, 1937, by Melvin DeGroote, Bernhard Keiser and CharlesM. Blair, Jr. If triethanolamine as employecl in the above formulas isreplaced by ethyl diethanolamine -or by diethyl ethanolamine, then onewould readily obtain the other two types of tertiary amines illustrated.Referonce is also made to copending application for patent, Ser. No.206,904, filed May 9, 1938, by Melvin DeGroote, Bernhard Keiser andCharles M. Blair, Jr.

In the remaining three types of materials there is at least one aminohydrogen atom present. The manufacture of such type material may beillustrated by the following reactions:

a n Similar reactions to the one immediately preceding result incompounds, such as: OH.R.COO.C:H 0H.R.C0O.C H; NH NH our canon,

This may be illustrated in the following manner:

diethanol ethylamine, diethanol encased ing at least one amino hydrogen,but one may employ the following reactions:

Naturally if ethyl ethanolamine or a similar amine were to replaceethanolamine (monoethanolamine), one would obtain the remaining type ofamine above illustrated.

Suitable hydroxy primary and secondary amines which may be employed toproduce materials of the kind above described include the following:diethanolamine, mcnoethanolamine, ethyl ethanolamine methylethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc.Other examples include cyclohexanolamine, dicyclohexanolamine,cyclohexyl ethanolamine, cyclohexyl propanolamine, benzyl ethanolamine,benzyl propanolamine, pentanolamine, hexanolamine, octyl ethanolamine,octadecyl ethanolamine, cyclohexanol ethanolamine. etc.

Similarly, suitable hydroxy tertiary amines which may be employedinclude the following: triethanolamine, diethanolalkylamines, such aspropylamine, etc. Other examples include diethanol methylamine,tripropanolamine, dipropanol methylamine, cyclohexanol diethanolamine,dicyclohexanol ethanolamine, cyclohexyl diethanolamine, dicyclohexylethanolamine, dicyclohexanol ethylamine, benzyl 'diethanolanune,dibenzylethanolamine, benzyl dipropanolamine, tripentanolamine,trihexanolamine, ethyl hexyl ethanolamine, octadecyl diethanolamine,polyethanolamine, etc.

It is also known that one may have amines of the type:

QHAOCaHlOH (311140 CzH OH CzHlOCrHrOH Such amines may serve asfunctional equivalents of the previously described amines.

All the amines of the kind above described and characterized by theformula:

\ m." in which n represents a small whole number, preferably less than10, and 111. represents the numeral 1, 2, or 3, m represents the numeral0, 1, or 2, and m" represents the numeral 0, 1, or 2 with the provisothat m+m'+m"=3, have four common characteristics. In the first place,

QJMAQB This is not the case in the compounds employed as intermediateraw materials for production of the compounds used as demulsifyingagents in the present process.

In the third place, it must be recognized that these compounds arederived only from basic amines. The word basic is employed to excludeamines having little or no basicity such as the ordinary aromatic aminesor any amine having at least one aryl radical directly joined to theamino hydrogen atom. For this reason, these amine products which areherein contemplated as demulsifying agents in the resolution ofpetroleum emulsions and which necessarily are characterized by freedomfrom any aryl groups as such, cannot be derived from aryl amines.

'They are derived solely from alkyl, alicyclic, or

aralkyl amines having at least one hydroxyl group present. It is truethat in the aralkyl amines there is an aryl group present, but it is'not directly attached to the nitrogen atom as in the case of aryl aminesbut in fact represents nothing more or less than a substituted alkylamine. For instance, we consider benzylamine as being the primary amine,phenmethyl amine.

Finally, it must be recognized that these materials have not lost anybasicity in the forms of the esterified amine and that they exhibit allthe properties of a basic amine, that is, they combine with water toform a base presumably a substituted ammonium compound, but notquaternary ammonium compounds insofar that there are always one, two orthree unsubstituted hydrogen atoms of the ammonium radical present. Theycombine with various acids to form salts. For example, they may becombined with acetic acid, hydrochloric acid, lactic acid, chloraceticacid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or anysuitable organic or inorganic acid, to form salts. It is understood thatthe reference in the specification and appended claims to the aminesincludes the basic form and the acid salts as well as the aminesthemselves. The characteristic demulsifying properties of the newcompositions of matter herein described are contributed in part by theamine, and it is immaterial whether the amine may be considered as beingin any one of the following forms:

in which T represents the substituents for the amino hydrogen atoms ofthe parent ammonia from which all amines are hypothetically derived andX simply represents the acid radical of any acid employed. Thisstatement applies with equal force and efiect to the final product, orcomposition of matter, which is also a basic amine of a more complextype.

Reference is again made to the formula which summarizes the variousaminesused as intermediate raw materials, viz.:

. (11).: on-acooomiom in which the characters have their previoussignificance.

Attention is directed to the fact that where the substituted alkvlradical OH.R.COO.C2H4 appears, a suitable non-aryl radical other than analiphatic residue may serve as the functional equivalent; forinstanceyanalicyclic radical derived from a cyclohexyl radical or an aralkylradical derived from a benzyl radical. In other words, in the heretoappended claims reference to the CBHZI radical as such or as an alkylradical or.residue is intended in the broad sense to include thealicyclic radicals or residues or the aralkyl radicals or residues whichare the equivalent thereof. .There is no intention to include anaromatic radical where there is a direct linkage between the aromaticnucleus and the amino hydrogen atom for the reason that such productshave little or no basicity and do not have the characteristic propertiesof the amines previously described.

In indicating the various hydroxylated tertiary amines of the -non-aryltype whichmay be employed to produce the amine contemplated as thedemulsifying agent of the present process, it is desirable to indicatethat amines of the type where a hydroxy acyl radical replaces a hydrogenatom of a hydroxyl radical of the hydroxy tertiary amine, are notincluded within the'broa'd class of hydroxy tertiary amines unless thereis another hydroxyl radical attached to the usual alkyl radical. Forinstance, if diethyl amino ethanol is treated with lactic acid so as toform lactyl ethanol diethylamine of the following formula:

then it is understood that such materials would not represent a hydroxytertiary amine within the meaning or scope as herein employed. If, onthe other hand, triethanolamine were treated with lactic acid 50 as; togive monolactyl triethanolamine -of the following composition:

then such compound would be included due to the presence of one or morehydroxyl radicals attached to the alkyl radicals.

Similarly, in indicating the various hydroxylated primary or secondaryamines of the nonaryl type which may be employed. to produce the aminecontemplated as the demulsifying agent of the present process, it isdesirable to inon o cmcn.o oo,mmm then it is understood that suchmaterials would not represent a hydroxy primary amine within the meaningor scope as herein employed. The same would be true of the correspondingproduct derived from diethanolamine, provided that ;both hydroxyradicals had been esterified with lactic acid. If on the other hand,diethanolamine were treated with lactic acid so as to give monolactyldiethanolamine of the following composition:

then such compound would be included due to the presence of the hydroxylradicals attached to the alkyl radicals. I

The manufacture of compounds from tertiary amines 'is relatively simplebecause no precautions are necessary to! prevent amidification. Theselected fatty oil and the selected hydroxy tertiary amine are mixed .insuitable proportions and heated at some point above the boiling point ofwater, for instance, 0., and at a point below the decomposition point ofthe amine or the fattty. oil, for instance, 180 0., for a suitableperiod of time, such as two to eight hours. Mild agitation is employed.A catalyst such as sodium oleate, sodium carbonate, caustic soda, etc.,may be present in amounts of about one-half of 1% or less. It is notedthat the fatty acids are employed in this instance in the form of anester, to wit, the glyceride, although as previously pointed out, otherfunctional equivalents can be readily employed with equal facility. Itis to be noted that the reactions above described do not take place toany appreciable extent if the fatty acid has been converted into thesoap or salt. Such salts are not functional equivalents.

When, however, one is employing a hydroxy primary or a hydroxy secondaryamine, precautions must be taken so that one gets a substantialpercentage of products derived by esterification rather thanamidiflcation. Any suitable ester may be employed, but it is often mostconvenient to use the glyceride, for instance, triricinolein.

The selected glyceride and the selected hydroxy primary or secondaryamine are mixed in suitable proportions and heated atsome point abovethe boiling point of water, for instance, 110C., and below thedecomposition point of the amine or fatty material, for instance, 180C., for a suitable period of time, such as four to twenty-four hours.Mild agitation is employed. A catalyst such as sodium oleate, sodiumcarbonate, caustic soda, etc., may be present in amounts of about /g% orless. It is to be noted that the fatty acids are present in ester formand not in the form of the free acid, and thus there .is no tendency toform the salt to any marked extent, and if conducted at the lower rangeof reaction temperatures, there is a decided tendency to form theesaisaaaa terification products rather than the, amidiflcation products.

In order to illustrate suitable examples of the amines which may be usedas intermediate raw materials the following examples are given:

Intermediate amine-Example 1 Castor oil is employed. For sake ofconvenience, its molecular weight is considered as being 925. Commercialtriethanolamine and castor oil in the proportion of one mole of castoroil to one mole of trlethanolamine are heated at a temperature betweenand C. for about 2 hours. Mild agitation is employed. The reactionproduct so produced may be used as such or may be converted into theacetate or other suitable form. The product is characterized by freedomfrom non-esterified alkylol radicals.

intermediate amine-Example 2 Ethyl dihydroxy stearate is reacted in theprevious manner with the various amines above enumerated in Examples 1and 2. in this case three moles of ethyl dihydroxy stearate are reactedwith one mole of the tertiary hydroxyamine.

Intermediate amine-Example 4 I Methyl hydroxy stearate is employed toreplace ethyl dihydroxy stearate in the examples indicated under Example3 above.

Intermediate amine-Example 5 Castor oil (triricinolein) is employed. Forconvenience its molecular weight is considered as being 925. Commercialdiethanolamine and castor oil in the proportion of two moles of castoroil to three moles of diethanolamine are heated at a. temperature of120-140 C. for about 12 hours. Mild agitation is employed. Loss ofbasicity is an indication of amidification. Time of reaction may beextended or temperature lowered or raised so as to insure maximumesterification. The reaction product so produced may be used as such ormay be converted into the acetate or other suitable form. The productshould be free from non-esterified alkylol radicals.

Intermediate amine-E:rample 6 Ethanolamine is substituted fordiethanolamine in Example 1, using three moles of ethanolamine for onemole of castor oil.

Intermediate amineE'xample 7 Ethyl ethanolamine is substituted fordiethanolamine in Example 1, using three moles of ethyl ethanolamine forone mole of castor oil.

Intermediate amine-Example 8 An other amine of the followingcomposition:

basic carboxy acid or its functlonalequivalent, such as the anhydride,with the proviso that such functional equivalent shall not include (a)the acid esters derived by reaction between a poly basic acid, such asphthalic acid or its anhydride,

and fats and generally have 8 or more carbon atoms and notover 32 carbonatoms. Common examples include oleic acid, stearic acid, linoleic acid,linolenic acid, ricinoleic acid, erucic acid, palmitic acid, etc. Thesevarious monohydroxy acids combine with alkali such as caustic soda,caustic potash, etc., to produce soap or soap-like materials and arecommonly referred to as mono- 25 basic carboxy detergent-forming acids.

These last mentioned classes of materials which are not contemplated inthe present invention are described in copending applications forpatents, .Ser. Nos. 211,036, filed May 31, 1938, by Melvin DeGroote, and211,038, filed May 31, 1938, by Melvin DeGroote.

The polybasic carboxy acids which may be employed, including some havingat least three carboxyl radicals, are phthalic, succinic, malic,fumaric, citric, maleic, adipic, tartaric, glutaric, diphenic,naphthalic, oxalic, etc.

Having prepared the intermediate amines above described, it is onlynecessary to react such amines with the selected polybasic carboxy acidor its functional equivalent in such a manner as to produce anesterified product as difierentiated from a salt. There is no objectionto salt formation, provided that esterification also takes place.

Composition of mutton-Example 1 Castor oil is reacted withtriethanolamine (see Example 1 in previous group of intermediate amineexamples), so as to produce material corresponding to (OH.R.COO.C2H4):N,in which H.R.C'OO represents the ricinoleic acid radical. One molecularWeight of this material is reacted with 3 molecular weights of phthalicanhydride.

This is a conventional esterification reaction, and the materials areintimately mixed and heated to approximately l20160 C. with constantagitation until samples taken from the batch and analyzed showsubstantially complete disappearance of the hydroxyl value andsubstantially no free phthalic anhydride. In event that the hydroxylvalue disappears and phthalic anhydride is still present, the amountshould be decreased to approximately 2% or 2 moles or thereabouts. Asuitable solvent may be present, and any water formed may be distilledoff continuously during the esterification process. The solvent mayremain behind in the final product or may be removed if desired. Ifdesired, the acidic mass may be neutralized with any suitable amine,such as triethanolamine, cyclohexylamine, triamylamine, etc.

Composition of -matter-Ea:ample 2 Butyl acid phthalate is substitutedfor phthalic anhydride in the previous example.

Composition of matter-Example 3 I Potassium acid phthalate issubstituted for phthalic anhydride in Composition of matter Example 1above.

Composition of matter-Example 4 The same procedure is followed as inComposition ofmatter-Example 1 above, except that no solvent isemployed, and when the reaction is complete, one to two moles orslightly less of glycerol are added and esterificatlon continued untilall the glycerol present is chemically combined.

Composition of matter-Example 5 Ethylene glycol is substituted forglycerol in Composition of matter-Example 4 immediately preceding.

Composition of matter-Example 6 Diethylene glycol is substituted forglycerol in Composition of matter-Example 4 immediately preceding.

Composition of matter-Example 7 The monoethyl ether derivative ofethylene glycol is employed in place of glycerol in Composition ofmatter-Example 4 above.

Composition of matter-Example 8 Octyl alcohol is substituted forglycerol in Composition of matter-Example 4 above.

Composition of matter Emample 9 Oleyl alcohol is substituted forglycerol inComposition of matterExample 4 above.

Composition of matter-Example 10 Maleic anhydride is substituted forphthalic anhydride in Composition of matter-Examples 1-9 inclusive.

Composition of matter-Example 11 Citric acid is substituted forphthalic-acid in Composition of matter-Examples 1-9 inclusive.

Composition of matterExample 12 As previously stated, the C2H4 radicalmay be any one of a number of hydrocarbon radicals which are aliphatic,alicyclic, or aralkyl in nature.

It is at once manifest that similar derivatives are available fromglycerols, polyglycerols, and the like, as indicated by the followingreaction:

It is not necessary to point out that the same types of reactions willproduce secondary or tertiary amines and that the reaction is notlimited to a combination with ammonia, but may take place with acombination of, other primary or secondary amines, such as amylamine,diamylamine, cyclohexylamine, dicyclohexylamine, benzylamine,dibenzylamine, amyl cyclohexylamine, etc.

This means that in the type of material previously described, there is awide variety of material, such as monoglycerylamine, diglycerylaor incase the hydroxyl OH.C3H5 radicals had been removed by csmine,monoglyceryl diethylamine, monoglyceryl dipropylamine, diglycerylpropylamine, triglycerylamine, etc., which are functional equivalents ofthe various amines previously described for reaction with triricinoleinand the like.' When such amines are employed instead of the radicalC1;Hzn appearing in a compound, one would have in place thereof theradical 'OH.CaHs; radical of these terificat-ion with any availablecarboxyl, then the substituent which replaces the CnH2nradical might'beindicated by the formula D.C3Hs. All that has been said here in regardto functional equivalents will be perfectly obvious with out furtherexplanation to those skilled in the art. See U. S. Patent No, 2,091,704,dated August 31, 1937, to Duncan and McAllister, and also U. S. PatentNo. 2,042,621, dated June 2, 1936, to Olin.

Similarly, it is evident that where reference is made to phthalic acid,some simple derivative, such as chlorinated phthalic acid, brominatedphthalic acid, methylated phthalic acid, or the like, would simply actas a functional equivalent. This applies not only to phthalic acid, butto all the dibasic acids enumerated. Similarly, it is evident that thereis no intention to differentiate between isomeric forms. One isomericform may serve as well as another.

We desire to emphasize that the products ob tained' in the aboveexamples may be used in the form of the amine by direct contact with theemulsion without contact with water. It may be contacted with water, i.e., in the form of a solution so as to produce in a greater or lesserdegree the'amine base, Furthermore, any of the products above describedmay be combined with a suitable acid. Acetic acid may be employed.Hydrochloric acid is particularly desirable. 1 In some instances acids,such as oleic acid or naphthenic acid, may be employed to give asuitable salt. As previously pointed out, any carboxylic hydrogen atommay be replaced by a suitable metallic atom or an organic radicalderived from an alcohol or from an amine. All such ionizable hydrogenatom equivalents are considered as the functional equivalent of theionizable hydrogen atoms themselves, and such neutralized forms areincluded in the scope of the appended claims as the equivalent of theacidic form. The expression fatty acid compound is employed to includethe acid itself, as well as salts and esters thereof. It is realizedthat where a free carboxy] and a basic amine residue exist in the samemolecule, there may be a tendency towards the formation of inner, saltscomparable to sulfanilic acid; but due to the size of the moleculeinvolved and perhaps for reasons of steric hindrance, we are not awarethat such inner salts are formed.

Briefly, then, the preparation of the composition of matter hereincontemplated depends on a reaction involving a polybasic carboxy acidbody, or its functional equivalent as described, and the complex amineof the kind described,

in such a. manner as to involve reactions other than salt formation. Inother words, the complex amines are basic in nature, and therefore couldreact with a polybasic acid to form a salt in a manner which, for sakeof convenience, W111 be indicated by a somewhat simpler reaction, thus:

mumooexnooonoflmNmooomcooNa COOP Such reactions are purelysaltformation. The materials of the kind herein contemplated, regardless oftheir nature, are of the kind obtained by reactions other than saltformation, and also other than amidification.

We desire to emphasize'that the expression polybasic carboxy acid as itappears in the claims refers not only to the acid itself, but to anyfunctional equivalent, such as the anhydride, the acyl chloride. a saltform having at least two free carboxyls, such as mono-sodium citrate,etc. It is also understood that in the hereto appended claims the natureof the final product is not limited to the form having a free carhoxylichydrogen atom, but that such free carboxylic hydrogen atom may actuallybe replaced by any functional equivalent of the kind previouslydescribed, for instance, a metallic atom, an ammonium radical, an amineradical, such as an amylamine radical, benzylamine radical, ethanolamineradical, diethanolamine radical, triethanolamine radical, a hydrocarbonradical, such as an ethyl, methyl, propyl, or arnyl radical, a radicalderived from ethylene glycol, glycerol, or the like; a cyclohexylradical, henzyl radical, etc. All such forms in which such ionizablehydrogen atom equivalent replaces an ionizable hydrogen atom, areobvious functional equivaventional nomenclature has been for purposes ofsimplicity and to show the similarity between certain reactions. 1

In the hereto appended claims, reference to the product derivedbyreaction between a 'polybasic carboxy acid body .of the kind previouslydescribed and an amine of "the kind previously described is meant torefer to suchproducts in all their various modifications previouslyreferred to, to -wit, such substances where carboxylic hydrogen atomsappear as such or have been replaced by metallic atoms, alkyl radicalsderived from various alcohols, amine radicals or residues, etc.; and asto the presence of any basic amine-nitrogen atom, it may be in the amineform or in salt form, or in a base form, as, for example, is obtainableby contact with water.

The functional equivalents of all these variations have been pointed outpreviously and are readily comprehended; and the scope of the claims inthe light of such obvious equivalents requires no further discussion.

As to blown oils, blown fatty acids, polymerized oils, polymerized fattyacids, and other similar materials obtainable by oxidation, it isunderstood that it is not intended that they should mediate amine whichin turn is reacted with a polybasic carboxy acid to produce the newcomposition of matter.

Conventional demulsifying agents employed in the treatment of oil fieldemulsions are used as such, or after dilution with any suitable solvent,such as water, petroleum hydrocarbons, such as gasoline, kerosene, stoveoil, a coal tar product, such as benzene, toluene, xylene, tar acid oil,cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols,such as methyl alcohol, ethyl alcohol, denatured alcohol, propylalcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may beemployed as diluents. Miscellaneous solvents, such as pine oil, carbontetrachloride, sulfur dioxide extract obtained in the refining ofpetroleum, etc., may be employed as diluents. Similarly, the material ormaterials employed as the demulsifying agent of our process may beadmixed with one or more of the solvents customarily used in connectionwith conventional 89 tively limited oil solubility. However, since suchreagents are sometimes used in a' ratio of 1 to 10,000 or 1 to 20,000,or even 1 to 30,000, such an apparent insolubility in oil and water isnot significant, because said reagents undoubtedly have solubilitywithin the concentration employed. This same fact is true-in regard tothe material or materials employed as the demulsifying agent of ourprocess.

We desire to point out that the superiority of the reagent ordemulsifying agent contemplated in our process is based upon its abilityto treat certain emulsions more advantageously and at a somewhat lowercost than is possible with other available demulsifiers, or conventionalmixtures thereof. It is believed that the particular demulsifying agentor treating agent herein described will find comparatively limitedapplication, so far as the majority of oil field emulsions areconcerned; but we have found that such a demulsifying agent hascommercial value, as it will economically break or resolve oil fieldemulsions in a number of cases which cannot be treated as easily or atso low a cost with the demulsifying agents heretofore available.

In practicing our process, a treating agent or demulsifying agent of thekind above described is brought into contact with or caused to act uponthe emulsion to be treated, in any of the various ways or by any of thevarious apparatus now generally used to resolve or break petroleumemulsions -with a chemical reagent, the above in which OHRCOO representsthe oxy-acyl radical derived from a hydroxylated fatty-acid; Trepresents a non-hydroxy hydrocarbon radical or the acylated-radicalobtained by replacing the hydrogen atom of the hydroxyl group of analkylol radical by the acyl radical of a monobasic carboxy acid havingless than 32 carbon atoms; n represents a small whole number which isless than 10; m represents the numeral 1, 2, or 3; 'm' represents thenumeral 0, l or 2, and m" represents the numeral 0, 1 or 2, with theproviso that m-i-m'+m" =3; and, second, a polybasic carboxy acidcompound characterized by: (a) the presence of at least one freecarboxy] radical; (b) the absence of any hydroxy fatty acid radical as asubstituent for an acidic hydrogen atom of any carboxyl radical; (c) theabsence of any polyhydric alcohol radical as a substituent for an acidichydrogen atom of any carboxy] radical if said polyhydric alcohol radicalis also united with one or more monobasic carboxy detergentforming acidradicals.

2. A composition of matter comprising products of the kind derivable byesteriflcation reaction between: First, an amine of the formula type inwhich OHRCOO represents the oxy-acyl radical derived from a hydroxylatedfatty acid; T represents a non-hydroxy hydrocarbon radical or theacylated radical obtained by replacing a hydrogen atom of the hydroxylgroup of an alkylol radical by the acyl radical of a monobasic (b) theabsence of any hydroxy fatty acid radical as a substituent for an acidichydrogen atom of any carboxy] radical; (c) the absence of any polyhydricalcohol radical as a substituent for an acidic hydrogen atom of anycarboxyl radical if said polyhydric alcohol radical is also united withone or more monobasic carboxy detergent-forming acid radicals.

3. A composition of matter comprising products of the kind derivable byesterification reaction between: First, an amine of the formula type fDw(on-nooo-oznom in which OH.RCOO represents the oxy-acyl radical derivedfrom a hydroxylated fatty acid; T

represents a non-hydroxy hydrocarbon radical or the acylated radicalobtained by replacing a hydrogen atom of the hydroxyl group of analkylol radical by the acyl radical of a monobas ic carboxy acid havingless than 32 carbon atoms; m represents the numeral 1, 2 or 3; mrepresents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or2, with the proviso that m+m'+m"=3; and, second, a polybasic carboxyacid compound characterized by: (a) the presence of at least one freecarboxy] radical; (b) the absence of any hydroxy fatty acid radiicalderived froma hydroxylated fatty acid; T

represents a non-hydroxy hydrocarbon radical; m represents the numeral1, 2 or 3; m represents the numeral 0, 1 or 2, and m" represents thenumeral 0,1 or 2, with the proviso that m+m'+m"=3; and, second, apolybasic carboxy acid compound characterized by: (a) the presence of atleast one free carbonyl radical; (b) the absence of any hydroxy fattyacid radical as a substituent for an acidic hydrogen atom of anycarboxyl radical; (c) the absence of any polyhydric alcohol radical as asubstituent for an acidic hydrogen atom of any carboxyl radical ifsaidpolyhydrlc alcohol radical is'also united with one or more monobasiccarboxy detergent-forming acid radicals.

5. A composition oi! matter comprising products of the kind derivable byesterification reaction between: First, an amine of the formula type(OH-RCOO.C2H4)mN(H)m', in which OH.RCO0 represents the oxy-acyl radicalderived from a hydroxylated fatty acid; m repre-. sents the numeral 1, 2or 3; m represents the numeral 0, 1 or 2, with the proviso that m+m=3;and, second, a polybasic carboxy acid compound characterized by: (a) thepresence of at least one free carboxyl radical; '(b) the absence of anyhydroxy fatty acid radical as a substituent for an acidic hydrogen atomof any carboxyl radical; (c) the absence of any polyhydric alcoholradical as a substituent for an acidic hydrogen atom of any carboxylradical if said polyhydric alcohol radical is also united with one ormore monobasic carboxy'detergent-forming acid radicals.

6nd, composition of matter comprising products of the kind derivable byesterification reaction between: First, an amine of the formula type(0H.RCo0.C2H4)niN(H)m', in which OHRCOO represents the oxy-acyl radicalderived from rioinoleic acid; m represents the numeral 1, 2 or 3; 111.represents the numeral 0, 1 or 2, with the proviso that m+m'=3; and,second, a polybasic carboxy acid compound characterized by: (a) thepresence of at least one free carboxyl radical; (b) the absence of anyhydroxy fatty acid radical as a substituent for an acidic hydrogen atomof any carboxyl radical; (c) the absence of any polyhydric alcoholradical as a'substituent for an acidic hydrogen atom of any carboxylradical if said polyhydric alcohol radical is also united with one ormore monobasic carboxy detergent-forming acid radicals.

7. A composition of matter comprising products of the kind derivable byesteriflcation reaction between: First, an amine of the formula type(OH.RCOO.C2H4) mNCH) m' in which OERCOO represents the oxy-acyl radicalderived from ricinoleic acid; 171. represents the numeral 1,, 2 or 3; mrepresents the numeral 0, 1 or 2, with the provisothat m+m=3;.and,

second, a phthalic acid compound characterized by; (a) thepresence of atleast one free, ca:r'-,

iooxyl radical; (b) the absence of any hydroxy fatty acid radical as asubstituent for an acidic hydrogen atom of any carboxyl radical; (c) theabsence of any polyhydric alcohol radical as a substituent'for an acidichydrogen atom of any carboxyl radical if said polyhydric alcohol radicalis also united with one or more monobasic car- 'boxy detergent-formingacid radicals.

8. A composition of matter comprising products of the kind derivable byesteriflcation reac- 1 tion between: First, an amine of the formula type(CH.RCOO.C2H4) mN(H)1n' in which OHRCOO represents the oxy-acyl radicalderived from ricinoleic acid; m represents the numeral 1, 2 or,3; mrepresents the numeral 0', 1 or 2, with the proviso that m+m'=3; and,second, phthalic anhydride.

9. A composition of matter comprising products of the kind derivable byesterification reaction-between: First, an amine of the formula type(OH.RCOO.C2H4) mN (H) m in which OI-LRCOO represents the oxy-acyl radiinwhich OHRCOO represents the oxy-acyi radical derived from ahydroxylated'fatty acid; '1 represents a non-hYdroxy hydrocarbon radicalor the acylated radical obtained by replacing the hydrogen atom of thehydroxyl group of an alkylol radical by the acyl. radical of a'monobasic carboxy acid having less than 32 carbon atoms; n represents asmall whole number which is less than 10; m represents the numeral 1, 2or 3; m represents the numeral 0, 1 or 2, and m" represents the numeral0, 1 or 2, with the proviso that m+m-|'-m"=3; and, second, a polybasiccarboxy acid compound characterized by: (a) the presence of at least onefree carboxyl radical; (b) the absence of any hydroxy fatty acid radicalas a substituent for an acidic hydrogen atom of any carboxyl radical;(c) the absence of any polyhydric alcohol radical as a. substituent foran acidic hydrogen atom of any carboxyl radical if said polyhydricalcohol radical is also united with one or more monobasic carboxydetergent-forming acid radicals.

11. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising products of the kind derivable by esteriflcationreaction between: First, an amine of the formula type (OH'RCOO'CIEII)II(Ti-w n in which OHRCQO, represents the oxy-acyl radical derived from ahydroxylated fatty acid; T represents a n'on-hydroxy hydrocarbon radicalor the acylated radical obtained by replacing a hydrogen atom of thehydroxyl group of an alkylol radical by the acyl radical of a monobasiccarboxy acid having less than 32 carbon atoms; CnHiln being an aliphaticradical; n represents a small whole number which is less than 112represents the numeral 1, 2 or 3; 112. represents the numeral 0, 1 or 2,and m" represents the numeral 0, 1 or 2, with the proviso thatm+m'+m"=3; and, second, a polybasic carboxy acid compound characterizedby: (a) the presence of at least one free carboxyl radical; (b) theabsence of any hydroxy fatty acid radical as a substituent for an acidichydrogen atom of any carboxyl radical; (c) the absence of any polyhydricalcohol radical as a substituent for an acidic hydrogen atom of anycarboxyl radical if said polyhydric alohol radical is also united withone ormore monobasic carboxy detergent-forming acid radicals 12. Aprocess for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising products of the kind derivable by esteriflcationreaction between: First, an amine of the formula type W in which OHRCOOrepresents the oxy-acyl radical derived from a hydroxylated fatty acid;T represents a non-hydroxy hydrocarbon radical or the acylated radicalobtained by replacing the hydrogen atom of the hydroxyl group of analkylol radical by the acyl radical of a monobasic carboxy acid havingless than 32 carbon atoms; m represents the numeral 1, 2 or 3; mrepresents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or2, with the proviso that m+m'+m"=3; and, second, a polybasic carboxyacid compound characterized by: (a) the presence of at least one freecarboxyl radical; (b) the absence of any hydroxy fatty acid radical as asubstituent for an acidic hydrogen atom of any carboxyl radical; (c) theabsence of any polyhydric alcohol radical as a substituent for an acidichydrogen atom of any carboxyl radical if said polyhydric alcohol radicalis also united with one or more monobasic carboxy detergent-forming acidradicals.

13. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifylngagent comprising products of the kind derivable by esteriflcationreaction between: First, an amine of the formula type In which OH.RCOOrepresents the oxy-acyl radical derived from a hydroxylated fatty acid;T represents a non-hydroxy hydrocarbon radical; m represents the numeral1, 2 or 3 111. represents the numeral 0, 1 or 2, and m" represents thenumeral 0, 1 or 2, with the proviso that and, second, a polybasiccarboxy acid compound characterized by: (a) the presence of at least onefree carboxyl radical; (b) the absence of any hydroxy fatty acid radicalas a substituent for an acidic hydrogen atom of any carboxyl radical;(c) the absence of any polyhydric alcohol radical as a substituent foran acidic hydrogen atom of any carboxyl radical if said polyhydricalcohol radical is also united with one or more monobasic carboxydetergent-forming acid radicals.

14. A process for breaking petroleum emulsions of the water-in-oil type,characterized by sub- (OH.RCOO.C2H4) "IN (H) m" in which OH.RCOOrepresents the oxy-acyl radical derived from a hydroxylated fatty acid;m represents the numeral 1, 2 or 3; m represents the numeral 0, 1- or 2,with the proviso that m+m" 3; and, second, a polybasic carboxy acidcompound characterized by: (a) the presence of at least one freecarboxyl radical; (1)) the absence of any hydroxy fatty acid radical asa substituen't for an acidic hydrogen atom of any carboxyl radical; (c)the absence of any polyhydric alcohol radical as a substituent foranacidic hydrogen atom of any carboxyl radical if said polyhydricalcohol radical is also united with one or more monobasic carboxydetergent-forming acid radicala,

15. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a de-.

mulsifying agent comprising products of the kind derivable byesteriflcation reaction between: First, an amine of the formula type(OH.RCOO.C2H4) mN(H) m' in which OHRCOO represents the oxy-acyl radicalderived from ricinoleic acid; m represents the numeral 1, 2 or 3; mrepresents the numeral 0, 1 or 2, with the proviso that m+m'=3; and,second, a polybasic carboxy acid compound characterized by; (a) thepresence of at least one free carboxyl radical; (b) the absence of anyhydroxy fatty acid radical as a substituent for an acidic hydrogen atomof any carboxyl radical; (c) the absence of any polyhydric alcoholradical as a substituent for an acidic hydrogen atom of any carboxylradical if said polyhydric alcohol radical is also united with one ormore monobasic carboxy detergent-forming acid radicals.

16. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising products of the kind derivable by esterificationreaction between: First, an amine of the formula type (OERCOOCzHa) mN(H) m' cal derived from ricinoleic acid; m represents the numeral 1, 2or 3; m represents the numeral 0, 1 or 2, with the proviso that m+m=3;and, second, a phthalic acid compound characterized by: (a) the presenceof at least one free carboxyl radical; (b) the absence of any hydroxyfatty 'acid radical as a substituent for an acldichydrogen atom of anycarboxyl radical; (c) the absence of any polyhydric alcohol radical as asubstituent for an acidic hydrogen atom of ,any carboxyl radical if saidpolyhydric alcohol radical is also united with one or more monobasiccarboxy detergent-forming acid radicals.

in which OHRdOO represents the oxy-acyl radi- V 17. A process forbreaking petroleum emulsions of the water-in-oil type, characterized bysubjecting the emulsion to the action of a demulsifying agent comprisingproducts of the kind derivable by esterification reaction betweenz' IFirst, an amine of the formula type lit (OH.RCOO.C2H4) mN (H) m'subjecting the emulsion to the action of a demulsifying agent comprisingproducts of the kind derivable by esteriflcation reaction between:First, an amine of the formula type- (OH.RCOO.C2H4) mN (H) m I in whichOHRCOO represents the oxy-acyl radical derived from ricinoleic acid; 172represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2,with the proviso that m+m=3; and, second, 9. glycerol acid phthalate.

MELVIN DE GROOTE. BERNHARD KEISER. CHARLES M. BLAIR, JR.

Certificate of Correction Patent No. 2,154,422.

April 18, 1939.

MELVIN DE GROOTE ET AL.

Itis hereby certified that error appears in the printed specification ofthe above numbered patent reqnlring correction as follows: Page 7, firstcolumn, lines 73 to 75 incluslve, 01mm 1, strike out the formula andinsert instead the followingand that the said Letters Patent should beread with this correction therein that the same may conform to therecord of the case in the Patent Oflice.

Signed and sealed this 6th day of June, A. D. 1939.

[SEAL] Henry Van Arsdale Acting Commissioner of Patents.

